Various high-performance wearable sensors have attracted increasing interest from researchers for the accurately monitoring of physiological signal. Wearable temperature sensors, as an important part of wearable sensors, allow accurate access to temperature information and are widely used in fields such as intelligent robotics and health monitoring. Improving key characteristics of wearable electronics is essential to expanding their application areas. In this study, we develop a wearable temperature sensor that leverages an ion capture and release dynamics mechanism, based on hydrogen bonding, to enhance the sensitivity of a wearable temperature sensor via a novel silica-in-ionogel composite. The developed sensor demonstrates ultra-high temperature sensitivity (0.008 °C) and excellent stability. Departing from conventional healthcare applications of physiological temperature monitoring, our work pioneers a novel paradigm to mirror our subjective thermal sensations, utilizing sensor data that exceeds the sensitivity of the human skin. As proof of concept, we demonstrate the sensor’s potential of apparent temperature monitoring for the purpose of establishing a smart dynamic temperature control system, with the aim of keeping the human in a thermally comfortable environment throughout. Our work opens up a potential application scenario for wearable temperature sensors in personalized temperature regulation.